US2995613A - Semiconductive materials exhibiting thermoelectric properties - Google Patents

Semiconductive materials exhibiting thermoelectric properties Download PDF

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Publication number
US2995613A
US2995613A US826594A US82659459A US2995613A US 2995613 A US2995613 A US 2995613A US 826594 A US826594 A US 826594A US 82659459 A US82659459 A US 82659459A US 2995613 A US2995613 A US 2995613A
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United States
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materials
lead
selenide
silver
telluride
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Expired - Lifetime
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US826594A
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English (en)
Inventor
Jack H Wernick
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AT&T Corp
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Bell Telephone Laboratories Inc
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Priority to NL253488D priority Critical patent/NL253488A/xx
Priority to NL113674D priority patent/NL113674C/xx
Application filed by Bell Telephone Laboratories Inc filed Critical Bell Telephone Laboratories Inc
Priority to US826594A priority patent/US2995613A/en
Priority to FR829959A priority patent/FR1259805A/fr
Priority to GB22721/60D priority patent/GB931008A/en
Priority to DEW28147A priority patent/DE1162436B/de
Priority to BE592719A priority patent/BE592719A/fr
Application granted granted Critical
Publication of US2995613A publication Critical patent/US2995613A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Definitions

  • FIG 4 N01. PER CENT PbTe 2 900 800 E 'u 700 u fi+ LIQUID u 3 a 500 q p g 400 l 300 k 200 E Q I00 it o l l I l I l l O 5O I00 AySbSe PbSe MOL PER CENT PbSe Pb Te IN VENTOR J. H. WERN/CK ATTORNEY 1961 J. H. WERNICK 2,995,613
  • thermoelectric power like the electrical resistivity of a material is a function of the level of n-type or p-type doping.
  • Thermal conductivity is relatively constant and is affected only little by such doping. A primary consideration in choosing a semiconductive material therefore is that the material exhibit a low thermal conductivity.
  • thermoelectric properties of lead telluride and lead selenide can be improved by introducing certain ternary compounds into the crystalline lattice of these binary compounds. More specifically, it has been found that silver antimony telluride, silver antimony selenide and silver bismuth selenide form a complete series of solid solutions with lead telluride or lead selenide. These solutions exhibit thermal conductivities of the same magnitude as those of the ternary compounds, in the order of 0.01 watt per centimeter per degree centigrade or less up to inclusions of about 90 percent of binary constituent. In this compositional range the thermoelectric power level characteristic of the binary material is retained or even improved. 4
  • FIG. 1 is a schematic front elevational view of a thermoelectric device utilizing materials described herein;
  • FIG. 2 is a schematic cross-sectional view of apparatus suitable for use in the preparation of the materials of the invention
  • FIG. 3 is a plot of thermal conductivity versus composition for binary-ternary solid solutions in accordance with the invention which illustrates the relationship between the concentration of the binary component and the thermal conductivity of the solid solution;
  • FIG. 4 plotted on coordinates of temperature versus mol percent lead selenide, is a phase diagram showing the lead selenide-silver antimony selenide system of the invention
  • FIG. 5 plotted on coordinates of temperature versus mol percent lead telluride, is a phase diagram showing the lead telluride-silver antimony selenide system of the invention
  • FIG. 6 plotted on coordinates of temperature versus molpercentleadselenidqisaphasediagramshowing Patented Aug. 8, 1961 2 the silver antimony telluride-lead selenide system of the invention
  • FIG. 7 plotted on coordinates of temperature versus mol percent lead telluride, is a phase diagram showing the silver antimony telluride-lead telluride system of the invention.
  • FIG. 8 plotted on coordinates of temperature versus mol percent lead selenide, is a phase diagram showing the silver bismuth selenide-lead selenide system of the invention.
  • FIG. 9 plotted on coordinates of temperature versus mol percent lead telluride, is a phase diagram showing the silver bismuth selenide-lead telluride system of the invention.
  • FIG. 10 is a quinary diagram on coordinates of mol percent showing the solid solution-forming regions of the constituents, lead selenide, lead telluride, silver bismuth selenide, silver antimony telluride and silver antimony selenide.
  • thermoelectric device 1 consists of semiconductive blocks 2 and 3, metal bar 4 and electrode contacts 5 and 6.
  • the circuit is completed by wires 7 and 8 and battery 9.
  • Metal bar 4 and electrodes 5 and 6 make low resistance, essentially ohmic contact to blocks 2 and 3 by means, for example, of a solder joint.
  • blocks 2 and 3 may be formed of materials of the instant invention.
  • blocks 2 and 3 may be formed of an n-type lead telluride-silver antimony telluride solid solution and a p-type lead telluride-silver antimony telluride solid solution, respectively, of the instant invention.
  • Exemplary device 1 utilizes two legs and dual heating and cooling junctions.
  • the device can, of course, be operated by using a single leg. schematically, this can be depicted by deleting block 2 and electrode 5 from de' vice 1 and extending wire 7 to bar 4 contacting a surface of block 3 opposite electrode 6.
  • FIG. 2 depicts one type of apparatus found suitable for the preparation of the materials of the instant invention. Reference is made to this figure in the examples related to the actual preparation of these materials.
  • the apparatus of this figure consists of a resistance wire furnace 25 containing two individual high resistance windings 26 and 28. These windings are turns of, for example, platinum-ZO percent rhodium resistance wire. In operation an'electrical potential is applied across terminals 29 and 30 by means not shown. The amount of current supplied to windings 26 and 28 is controlled by auto-transformer 34.
  • sealed container 36 having an inside diameter in the order of, for example, 19 millimeters within which 'there is scaled a second crucible 37 containing the ingredients 38 used in the synthesis of a material of this invention.
  • Containers 36 and 37 are inert with respect to the ingredients under the processing conditions. Silica containers have been found to be satisfactory. Container 36 completely encloses container 37 thereby preventing possible loss by vaporization of the component materials during processing.
  • Crucible 37 may preferably have a coating 39 of, for example, carbon on its inside surface to reduce adhesion between crucible 37 and the final material.
  • Inner crucible 37 is closed at its upper end with an inert cap 40, for example, made of graphite having venting hole 41 which permits the equalization of pressure in containers 36 and 37. Cap 40 possible boiling over into the container 36 of the component materials 38 during processing. Further, cap 40 minimizes heating of materials 38 during the sealing off of container 36, which might cause some volatilization and accompanying loss of the materials 38. vaporization losses by condensation during processing are minimized by use of insulation layers 43 and 44 made of a refractory silicate such as Sil-ocell refractory. 7
  • Inner surface of crucible 37 is coated with a carbon layer 39 by exposing the crucible to a mixture of four parts of nitrogen and one part of methane for a period of fifteen minutes and a flow rate of approximately 250 cubic centimeters per minute with the crucible at a term perature of about 1000 C.
  • the nitrogen gas aids in the formation of a uniformly thin carbon layer.
  • the component materials 38 are placed in crucible 37 which is then stoppered with cap 40 and placed within container 36.
  • Outer container 36 is then evacuated, filled with tank nitrogen at a pressure of two-thirds of an atmosphere, sealed and placed within furnace 25.
  • the nitrogen atmosphere aids in retarding volatilization of-the initial components.
  • the partial vacuum inside crucible 36 aids in the sealing of the top of the crucible by causing it to collapse inwardly and come together when the crucible is heated in this region.
  • An electrical potential is then applied across terminals 29 and 30 and auto-transformer 34 is adjusted so as to result in furnace temperature within windings 26 and 28 of about 1125' C.
  • This temperature is arbitrary and is dependent only upon the temperature required to melt component materials 38.
  • lead selenide which has the highest melting point of any of the constituent materials of the instant invention melts at approximately 1080 C. Temperatures higher than 1125 C. are limited only by economic conditions and furnace capabilities. Since the terminal portions of the furnace are at a hotter temperature than the central portion, dynamic loss by vaporization and condensation of the component materials 38 is prevented.
  • Heating of the furnace is gradual, taking about four hours from room temperature to the high temperature of 1125 C. so that the major portion of the alloying is carried out over a range of temperature at which the vaporization pressure of the component materials is relatively low thereby minimizing loss.
  • Heating is continued for four hours to insure adequate mixing and diffusion of the reactants which in turn insures a homogeneous end product.
  • the melt is then permitted to furnace cool to room temperature. Since thermoelectric devices in general use polycrystalline materials, the rate of cooling is not critical. Resortnced not be had to slow cooling rates to obtain single crystals. From this standpoint there is no objection to turning oi the furnace power and allowing the melt to cool naturally or removing the melt from the furnace and rapidly cooling it.
  • EXAMPLE 3 A solid solution having formula was prepared as above using a mixture of 12.14 grams of silver, 13.70 grams of antimony, 17.77 grams of selenium, 7.77 grams of lead and 4.79 grams of tellurium.
  • EXAMPLE 4 A solid solution having formula was prepared as above using a mixture of 5.39 grams of silver, 10.45 grams of bismuth, 19.74 grams of selenium and 31.08 grams of lead.
  • thermoelectric measurements made on the materials of Examples 1-6 and other materials of the present invention are listed in Table I. Values for the binary materials herein discussed are indicated, not as part of the invention, but for comparative purposes. As can be seen, certain of these materials exhibit thermoelectric o powers higher than those of the binary and ternary end components.
  • FIG. 3 depicts a plot of thermal conductivity versus lead telluride concentration for a typical material of the invention, a silver antimony telluride-lead telluride solid solution.
  • Lead telluride and lead selenide exhibit thermal conductivities in the order of 0.02 watt per centimeter per degree centigrade.
  • Silver antimony telluride, typical of the ternary compounds herein discussed exhibits a thermal conductivity in the order of 0.006 watt per centimeter per degree centigrade.
  • inclusions of as little as ten percent of the ternary compound in the binary compound result in a fifty percent decrease in the thermal conductivity of the binary compound. Such inclusion constitutes a preferred range of the ternary-binary solid solutions of the instant invention.
  • the thermal conductivity of the ternary compound is substantially retained with as little as twenty percent inclusion of the ternary into the binary component.
  • inclusion therefore constitutes an optimum composition range for the ternary-binary solid solutions of the invention.
  • inclusions of five percent binary compound in the ternary compound result in a lattice constant measurably difierent from the pure ternary.
  • a preferred solid solution composition of the invention therefore includes from five to ninety percent of the binary compound.
  • An optimum composition includes from five to eightly percent of the binary compound.
  • FIGS. 4, S, 6, 7, 8 and 9 are phase diagrams of materials of the present invention. Differential thermal analyses were made to determine the liquidus, solidus and solid state transformation temperatures. These diagrams show that the materials herein contemplated are single phase solid solutions, the high temperature forms of which have the disordered sodium chloride type structure, designated beta.
  • beta disordered sodium chloride type structure
  • FIG. 10 is a plot showing the solid solution-forming regions of the binary and ternary compounds herein discussed. It has previously been shown that the compounds connected by legs 1 through 6 form a complete series of solid solutions.
  • FIG. 3 is considered exemplary of any of the systems of FIG. 10. As such, the scope of the instant invention is not limited to any particular ternary-binary solid solution but rather includes any of the solid solution systems of FIG. 10.
  • the extrinsic semiconductive properties of any one of the materials herein disclosed may be changed by doping in accordance with accepted doping procedure.
  • the conductivity type of any of the materials of the instant invention may be caused to approach n-type by substitution of any one of the elements of the material by any element having a larger number of electrons in its outer ring.
  • the conductivity type may be caused to approach p-type by substitution with an element having a smaller number of electrons inits outer ring.
  • thermoelectric devices Semidegenerate behavior is desirable. Therefore the materials of the invention are considered operative at levels of 0.1 percent significant impurity and higher.
  • a homogeneous semiconductive composition consisting essentially of at least about 5 mol percent to about 90 mol percent of one binary compound selected from the group consisting of lead telluride and lead selenide, remainder at least'one ternary compound selected from the group consisting of silver antimony telluride, silver antimony selenide and silver bismuth selenide.
  • a semiconductive' composition in accordance with claim 1 consisting essentially of about 5 mol percent to about-80 mol percent of at least one of said binary compounds.
  • thermoelectric device comprising a first element having a composition consisting essentially of at least from about 5 mol percent to about 90 mol' percent of one binary compound selected from the group consisting of The compounds connected by legs 8, 9
  • lead telluride and lead selenide remainder at least one ternary compound selected from the group consisting of silver antimony telluride, silver antimony selenide and silver bismuth selenide, said composition forming a low resistance, essentially ohmic junction with another element having a dilferent conductivity mechanism.
  • thermoelectric device in accordance with claim 4 wherein said composition consists essentially of about 5 mol percent to about mol percent of at least one of said binary compounds selected from the group consisting of lead telluride and lead selenide.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
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US826594A 1959-07-13 1959-07-13 Semiconductive materials exhibiting thermoelectric properties Expired - Lifetime US2995613A (en)

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Application Number Priority Date Filing Date Title
NL253488D NL253488A ( ) 1959-07-13
NL113674D NL113674C ( ) 1959-07-13
US826594A US2995613A (en) 1959-07-13 1959-07-13 Semiconductive materials exhibiting thermoelectric properties
FR829959A FR1259805A (fr) 1959-07-13 1960-06-14 Matière semi-conductrice présentant des propriétés thermo-électriques
GB22721/60D GB931008A (en) 1959-07-13 1960-06-29 Improvements in or relating to semiconductive materials
DEW28147A DE1162436B (de) 1959-07-13 1960-07-06 Thermoelektrische Anordnung
BE592719A BE592719A (fr) 1959-07-13 1960-07-07 Matériaux semi-conducteurs à propriétés thermoélectriques.

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US826594A US2995613A (en) 1959-07-13 1959-07-13 Semiconductive materials exhibiting thermoelectric properties

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061657A (en) * 1960-12-07 1962-10-30 Rca Corp Thermoelectric compositions and devices utilizing them
US3073883A (en) * 1961-07-17 1963-01-15 Westinghouse Electric Corp Thermoelectric material
US3249469A (en) * 1960-10-22 1966-05-03 Philips Corp Semiconductive material, semiconductive and thermoelectric devices
FR2532786A1 (fr) * 1982-09-03 1984-03-09 Ecd Anr Energy Conversion Co Nouvelles matieres thermo-electriques en poudre comprimee et procede pour leur realisation
US4447277A (en) * 1982-01-22 1984-05-08 Energy Conversion Devices, Inc. Multiphase thermoelectric alloys and method of making same
EP1129473A2 (en) * 1998-10-13 2001-09-05 Board of Trustees operating Michigan State University Conductive isostructural compounds
US20050076944A1 (en) * 2003-09-12 2005-04-14 Kanatzidis Mercouri G. Silver-containing p-type semiconductor
US20070107764A1 (en) * 2003-09-12 2007-05-17 Board Of Trustees Operating Silver-containing thermoelectric compounds
CN112607714A (zh) * 2021-01-07 2021-04-06 安徽大学绿色产业创新研究院 一种PbSe基热电材料的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2811570A (en) * 1954-12-15 1957-10-29 Baso Inc Thermoelectric elements and method of making such elements
US2882468A (en) * 1957-05-10 1959-04-14 Bell Telephone Labor Inc Semiconducting materials and devices made therefrom

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685608A (en) * 1951-11-02 1954-08-03 Siemens Ag Thermoelement, particularly for the electrothermic production of cold
DE1059940B (de) * 1956-07-31 1959-06-25 Toho Dentan Kabushiki Kaisha Wismut-Tellur-Thermoelement zur elektrothermischen Kaelteerzeugung
GB834593A (en) * 1956-12-18 1960-05-11 Gen Electric Co Ltd Improvements in or relating to thermocouples

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2811570A (en) * 1954-12-15 1957-10-29 Baso Inc Thermoelectric elements and method of making such elements
US2882468A (en) * 1957-05-10 1959-04-14 Bell Telephone Labor Inc Semiconducting materials and devices made therefrom

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249469A (en) * 1960-10-22 1966-05-03 Philips Corp Semiconductive material, semiconductive and thermoelectric devices
US3061657A (en) * 1960-12-07 1962-10-30 Rca Corp Thermoelectric compositions and devices utilizing them
US3073883A (en) * 1961-07-17 1963-01-15 Westinghouse Electric Corp Thermoelectric material
US4447277A (en) * 1982-01-22 1984-05-08 Energy Conversion Devices, Inc. Multiphase thermoelectric alloys and method of making same
FR2532786A1 (fr) * 1982-09-03 1984-03-09 Ecd Anr Energy Conversion Co Nouvelles matieres thermo-electriques en poudre comprimee et procede pour leur realisation
US4588520A (en) * 1982-09-03 1986-05-13 Energy Conversion Devices, Inc. Powder pressed thermoelectric materials and method of making same
EP1129473A4 (en) * 1998-10-13 2004-03-17 Univ Michigan State CONDUCTIVE ISOSTRUCTURAL COMPOUNDS
US6312617B1 (en) * 1998-10-13 2001-11-06 Board Of Trustees Operating Michigan State University Conductive isostructural compounds
EP1129473A2 (en) * 1998-10-13 2001-09-05 Board of Trustees operating Michigan State University Conductive isostructural compounds
USRE39640E1 (en) * 1998-10-13 2007-05-22 Board Of Trustees Operating Michigan State University Conductive isostructural compounds
EP2009672A1 (en) * 1998-10-13 2008-12-31 Board of Trustees operating Michigan State University Conductive isostructural compounds
EP2068348A1 (en) * 1998-10-13 2009-06-10 Board of Trustees operating Michigan State University Conductive isostructural compounds
US20050076944A1 (en) * 2003-09-12 2005-04-14 Kanatzidis Mercouri G. Silver-containing p-type semiconductor
US20070107764A1 (en) * 2003-09-12 2007-05-17 Board Of Trustees Operating Silver-containing thermoelectric compounds
US7592535B2 (en) 2003-09-12 2009-09-22 Board Of Trustees Operating Michingan State University Silver-containing thermoelectric compounds
US8481843B2 (en) 2003-09-12 2013-07-09 Board Of Trustees Operating Michigan State University Silver-containing p-type semiconductor
CN112607714A (zh) * 2021-01-07 2021-04-06 安徽大学绿色产业创新研究院 一种PbSe基热电材料的制备方法
CN112607714B (zh) * 2021-01-07 2023-07-25 安徽大学绿色产业创新研究院 一种PbSe基热电材料的制备方法

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GB931008A (en) 1963-07-10
NL253488A ( )
NL113674C ( )
DE1162436B (de) 1964-02-06

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